Anthraquinone reactive dyestuffs

ABSTRACT

ANTHRAQUINONE REACTIVE DYESTUFFS USEFUL IN DYEING HYDROXYL AND NITROGEN-CONTAINING TEXTILES HAVING A NUCLEUS CONSISTING OF A SUBSTITUTED OR UNSUBSTITUTED 1-AMINO-2SULFO-4 (SUBSTITUTED OR UNSUBSTITUTED (4&#39;&#39;-AMINO- OR ALKYLENE AMINO-TRIAZINYL) ANALINO) ANTHRAQUINONE. THE DYESTUFFS SHOW IMPROVED FASTNESS PROPERTIES.

Int. 067a 55/46 US. Cl. 260-249 13 Claims ABSTRACT OF THE DISCLOSUREAnthraquinone reactive dyestuffs useful in dyeing hydroxyl andnitrogen-containing textiles having a nucleus consisting of asubstituted or unsubstituted 1-amino-2- sulfo-4 [substituted orunsubstituted (4-aminoor alkylene amino-triazinyl) analino]anthraquinone. The dyestuffs show improved fastness properties.

The invention relates to valuable new anthraquinone reactive dyestuffsof the formula NH- (CH2).,1TI-lNJ-Rg R Re R (I) In this formula R and Rrepresent, independently of one another, hydrogen or substituents, Rstands for a substituent, R to R stand, independently of one another,

for hydrogen or substituents, n is the number 0, 1 or 2, R

stands for hydrogen or for a substituent, R stands for an amino orhydrazino group or for a hydrocarbon radical which may be linked via 0,N or S and which may be further substituted, and F stands for a fluorinesubstituent.

Suitable substituents R R or R are, for example, hydroxyl, amino andsulphonic acid groups. The left nucleus of the anthraquinone moleculecontains by definition, at least one substituent R i.e., for example, asulphonic acid, an amino or a hydroxyl group. Valuable dyestuffs areespecially those which contain a sulphonic acid group in the 5-, 6-, 7-or 8-position and contain one or two hydroxyl and/0r amino groups in the5- and/or 8- position. The amino groups may exhibit furthersubstituents, particularly hydrocarbon radicals, such as methyl, ethylor propyl groups; or aryl groups, such as phenyl radicals andsubstituted phenyl radicals, for example, 0, m or p-toluyl radicals; andsulphophenyl radicals.

Suitable substituents R R R or R, are, for example, sulphonic acid,alkyl, alkoxy or halogen substituents. Of the alkyl groups, particularlylower alkyl groups, such as methyl and ethy substituents, in theo,o'-position to the NH group or in the 0-, mor p-position to the NHgroup are preferred. One-group of vauable dyestuffs contains, assubstituents R R R or R one or two sulphonic acid groups in the o-, niofp-position or in the 2,4- or 2,5- position to the NH group of the phenylnucleus.

Of the substituents R, especially lower alkyl groups, such as methyl andethyl groups, are preferred.

Suitable radicals R on the carbon atom of the triazine ring are thefollowing: NH substituted amino groups, such as NHCH -N(CHs)2, NHC H-N(C H NHC H NH-C H arylamino United States Patent 0 Patented Jan. 26,1971 groups, such as phenylamino groups and substituted phenyl-aminogroups, eg o-, mor p-sulphophenyl-amino groups 2,4-, 2,5- and3,5-disulphophenylamino, 0-, mor p-chlorophenylamino, o-, mor p-methylhenylamino, p-nitrophenylamino groups; ether and thioether groups, suchas methoxy, ethoxy, propoxy, phenoxy and substituted phenoxy radicals;meth'ylthio, ethylthio and phenylthio groups as well as substitutedphenylthio groups; hydrocarbon radicals, such as lower alkyl groups,e.g., methyl, ethyl and propyl radicals; or aryl radicals, such asphenyl and substituted phenyl radicals; e.g., chlorophenyl,methylphenyl, nitrophenyl :and sulphophenyl radicals.

Suitable triazine rings NAN w 0 NH2 R1 H SOaH R U l R u I 3 NH 0112)..NH

R, R7 in in which R to R and n brave the same meaning as above, withfluorotriazine compounds of the formula ey 8 (IV) in which R, and F havethe same meaning as above and X stands for an anionically splittableradical.

The fluorine substituent has a preferred interest among the reactivesubstituents X which can be split ofi an anionic radicals. Furtheranionically splittable radicals which are suitable, as the case may be,are quaternary ammonium groups, such as -N(CH3)3 and ---N (02 5)? forexample.

According to another method of production, the new dyestuffs areobtained in such a manner that anthraquinone dyestuffs of the formula NH1 I l S 03H F R l A R4 R5 N N Rt 11 1 0 NH ---(CHz) n I N X R5 R7 R inwhich R to R n and F as well as X have the same meaning as above,

are condensed, for example, with ammonia or amino, hydroxy or thiocompounds which contain a reactive hydrogen atom, While splitting offHX. In this way dyestuffs are obtained in which the substituent R of theproducts of the Formula I stands, for example, for an amino group or fora hydroxy ether or thioether grouping, which are linked with the carbonatom of the triazine ring via the O or S atom.

Triazine compounds suitable for the above-mentioned reactions are thefollowing, for example: 2,4,6-sym.-trifluoro-triazine,2,4-difluoro-6-amino-sym.-triazine,2,4-difluoro-6methylamino-sym.-triazine, 2,4difluoro-6-ethylamino-sym.-triazine, 2,4 difluoro-6-phenylamino-sym.-triazine, 2,4 difluoro-6-(2'- or 4'- or 6'-sulphophenyl)-amino-sym.-triazine, 2,4-difluoro-6-(2',4'- or 3,4'- or 2',5'- or4,5'-disulphophenyl)amino-sym.-triazine, 2,6-difluoro.4-dimethylamino-triazine, 2,6-difiuoro-4-methoxy-triazine,2,6-difluoro-4-(fl-methoxy-ethoxy)triazine, 2,6 difluoro- 4 hydrazinotriazine, 2,6-difluoro4-phenoxy-triazine, 2,6-difluoro-4-(2-, 3- or4-sulphophenoxy)-triazine, 2,6-difluoro 4 benzyloxy-triazine,2,6-difluoro-4-(fl-hydroxyet-hylmercapto-triazine,2,6-difluoro-4-methyl-triazine, 2,6- difluoro-4-phenyl-triazine,2-6-difluoro-4-(2'-, 3- or 4'- sulphophenyl) triazine,2,6-difiuoro-4-ethylmercapto-triazine, 2,6difluoro-4-(p-hydroxyethylamino)-triazine, 2,6-

difluoro 4 methyl-mercapto-triazine, 2,6-difluoro-4-phenylmercapto-triazine, 2,6 difluoro 4-(2-, 3- or 4'- chlorophenylmercapto)-triazine or 2, 6-difluoro-4-(2'-, 3- or4-sulphophenylmercapto)triazine.

The above-mentioned and further fluorotriazine compounds which can beused according to the invention can, in general, readily be obtained byreacting the appropriate chlorine or bromine compounds with alkali metalfluorides, e.g., with potassium fluoride, NaHF, KSO F, SOF and AgF or byreacting the appropriate OH compound with SP COF COClF or cyanofluoride,or by heating appropriate diazonium tetrafluroborates.

The reaction of the a-mino-anthraquinone compounds with heterocycliccomponents (IV) and the reaction of dyestuffs of the Formula V with, forexample, amino, hydroxy or thio compounds is carried out, dependent uponthe type of the starting compounds used, in an organic, organic-aqueousor aqueous medium at temperatures ranging from 10 C. to 100 (3.,preferably from 0 C. to 50 C., in the presence of alkaline condensingagents, such as aqueous alkali metal carbonate or alkali metal hydroxidesolutions.

A further modification for the preparation of the new dyestuffs of theFormula I, which may be applied in some cases, consists in that inamino-anthraquinone dyestuffs of the formula 0 NH; R1 H I A soin F R H\l/Ri R5 N] N a 0 M3 -t- N R6 R1 R (v1) in which R to R and n have thesame meaning as above,

and

Y represents an anionically splittable radical with the exception of afluorine substituent,

Y is exchanged in known manner for a fluorine substituent.

The exchange of a substituent Y, e.g., of the chlorine or bromine atomsfor fluorine substituents, can be carried out in the manner alreadydescribed.

Some of the anthraquinone reactive dyestuffs obtainable according to thevarious methods described may also subsequently be sulphonated, e.g.,with the aid of oleum.

The new dyestuffs are extremely valuable products which are suitable forthe greatest variety of purposes of application. In the form ofWater-soluble compounds, they have a preferred importance for the dyeingof hydroxyl group-containing and nitrogen-containing textile materials,in particular of textile materials obtained from natural and regeneratedcellulose as well as of wool, silk, synthetic polyamide and polyurethanefibres. Due to the reactive fluorine substituent or substituents in thetriazine ring, the products are especially well suited as reactivedyestuffs for the dyeing of cellulose materials according to the methodswhich have recently become known for this purpose. The fastnessproperties obtained are excellent, in particular the fastness to wetprocessing.

For the dyeing of cellulose, the dyestuffs are preferably used in anaqueous solution which can be mixed with alkaline reacting substances,such as alkali metal hydroxide or alkali metal carbonate, or withcompounds which are converted into alkaline reacting substances, such asalkali metal bicarbonate, Cl C-COONa. Further auxiliary agents may beadded to the solution, but these should not react with the dyestuffs inan undesirable manner. Such additives are, for example, surface-activesubstances, such as alkylsulphates, or materials or dyeing auxiliaryproducts preventing the migration of the dyestuff, such as urea, orinert thickening agents, such as oil-in-water emulsions, tragacanth,starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to bedyed, for example, by padding on the foulard (short bath) or byprinting, followed by heating for some time to an elevated temperature,preferably to 40 to 150 C. Heating may be carried out in the hot flue,in a steam apparatus, on heated rollers, or by the introduction intoheated concentrated salt baths, either alone or successively in anydesired sequence.

When a padding or dyeing liquor without alkali is used, a passage of thedry material is subsequently carried out through an alkaline-reactingsolution to which common salt or Glauber salt is added. The saltaddition thus reduces the migration of the dyestuff from the fibre.

It is also possible to pretreat the material to be dyed with acidbinding agents mentioned above, subsequently treating it with thesolution or paste of the dyestuff and finally, as stated, fixing it atan elevated temperature.

When dyeing is carried out from a long bath, the material is introducedat room temperature into an aqueous solution of the dyestuff(goods-to-liquor ratio 1:5 to 1:40, and dyed for 40 to minutes, whileoptionally raising the temperature up to 20 to 60 C., with theportionwise addition of salt, e.g., sodium sulphate, and subsequently ofalkali, for example, sodium phosphates, sodium carbonate, NaOH or KOH.

In this way, a chemical reaction takes place between the dyestuff andthe fibre. When the chemical fixation is completed, the dyed material isrinsed hot and finally soaped, non-fixed resides of the dyestuff thusbeing removed. Eminently fast dyeings, which are especially fast to wetprocessing and light, are obtained.

In the so-called cold-bath-padding process a subsequent heating of thepadded :fabric may be dispensed with by storing the fabric at roomtemperature for some time, e.g., for 2 to 20 hours. A stronger alkali isused in this process than that which has been used in the dyeing processfrom a long bath described above.

For printing materials containing hydroxy groups, a printing paste isused consisting of the dyestuff solution, a thickening agent, such assodium alginate, and a compound of alkaline reaction or splitting offalkali upon heating, such as sodium carbonate, sodium phosphate,potassium carbonate, potassium acetate or sodium and potassium hydrogencarbonate, and the printed material is rinsed and soaped.

Textile materials containing amide groups, such as wool, silk, syntheticpolyamide and polyurethane fibres, are generally dyed in the acidic orneutral range according to the dyeing methods customary for thispurpose, a final increase of the pH value of the dyebath, e.g. to pH 7to pH 9, sometimes being of advantage.

The dyestuffs are applied, for example, to wool and silk in the form ofsolutions, and to synthetic polyamide fabrics in the form of solutionsor, preferably, in a dispersed form followed by an aftertreatment,optionally together with acid-binding agents (preferably in rather smallamounts), such as sodium carbonate. Particularly favourable results areobtained on synthetic superpolyamides with those dyestuifs which areinsoluble or only sparingly soluble in water. These are worked up byconventional methods and with the addition of the known auxiliary agentsinto a dyestuffs dispersion and used as such in the dye'bath and/orpadding bath or in a printing paste. Auxiliary agents suitable for beingused in this way are inter alia compounds which prevent the dyestutf tomigrate from the fibre, such as cellulose ethers, alkali metal chloridesand sulphates; wetting agents, such as condensation products fromethylene oxide and fatty al cohols or phenols, sulphonated fattyalcohols; solvents, such as thiodiglycol, as well as thickening agents,such as starch, tragacanth, alginate thickening, gum arabic etc.

The aftertreatment of the dyeings, impregnations and prints obtained onpolyamide fabrics is preferably carried out at a temperature of 50 to110 C. and for a period of time ranging from to 60 minutes.

The dyeings obtainable with the new dyestuffs are generallydistinguished by good to very good fastness properties, especially by anexcellent fastness to wet processing.

The parts in the following examples are parts by weight.

In an analogous manner, the amino-anthraquinone derivatives set out inthe following Table can be converted into valuable reactive dyestulfs,the shades of which on cotton are indicated:

Water-soluble amino-anthraquinone derivative Shade 1-amino-4Q-N-methylaminomethylanilinc)- Greenish anthraqulnone2,6,2-trisulphonicacid. blue. l-ammo-4-(4-N-methylaminomethylanilino)- D0.anthraquinoneZ,5,8-trisulphonic acid.

l-amino4:(4-N-methylaminomethylanllino)- Blue.

anthraqumone-2,S-disulphonic acid.l-ammod-(4-aminoanilino)-anthraquinone-- Blue-green. 2,6-d1snlphonicacid. l-amino--(4-arnlnoanilino)-anthraquinone- Greenlsh 2,541isulphonicacid. l-amin0-4-(3-aminoanilino)-anthraquinone-- Blue. 2,6-disulphonicacid.

1-amlno-4-(3aminoanilino)-anthraquinone- Do.

2,5-disulphonic acid.

EXAMPLE 2 9.5 parts1-amino-4-(4'-aminophenylamino)-anthraquinone-2,'6,2'-trisulphonic acidare dissolved in 95 parts of water followed by the dropwise addition ofto C. of 2,4-difluoro-6-B-methoxyethoxy)-triazine. The pH value ismaintained at 6m 7. When the reaction is com- 25 pleted, theprecipitated product is filtered off with suction and washed with acommon salt in solution. It is dried at to C. in a vacuum.

The dyestulf has the following constitution:

In an analogous manner further valuable reactive dyestufis can beproduced from the components set out in the following Table, which dyewool and cotton in the specified shades:

Dyeing compound Reactive group Shadel-amino-4-(4'-aminophenylarnino)-anthraquinone-2,6,3"trisulphonio acid2I4 difiu0ro.6methoxy-triazine'l'amino-4-(4-N-methyl-aminomethyl-anilino)-anthraquinone:2,7,2'-trisulphoca l-am in0-4-(4-aminoani1ino)-anthraquinone-2,7-d1su1phonie acid2,4-ditluoro6-methylmercapto-triazine Greenish blue.2,4-difluoro-fi-diethylaminotriazine B lue-green.

EXAMPLE 1 63 parts 1 amino-4-(4-aminophenyl)aminoanthraquinone-2,5,S-trisulphonic acid are dissolved in 630 parts ofwater and the pH is adjusted to 6 with a sodium hydroxide solution; 22parts 2,4-difluoro-6-B-methoxyethoxytriazine are then added dropwise at0 to 5 C., and a pH of 6 to 7 is maintained with a sodium carbonatesolution. When the reaction is completed, the product is salted out withpotassium chloride, filtered off with suction and washed with a 20%potassium chloride solution. The dyestufl'obtained in the form of smallbluegreen needles is dried at 30 to 40 C. in a vacuum. It probablycorresponds to the following formula H 038 (I? IITH;

SOaH

and dyes cotton in greenish blue shades.

EMMPLE 3 6.1 parts l-amino-4-(3-aminomethyl-2',6-dimethyl-(anilino)-anthraquinone-2,6,5'-trisulphonic acid are dissolved in 65parts of water and acylated at a pH value of 6 with 3 parts2,4-difluoro-6-ethoxy-triazine. The pH value is adjusted with a 2 Nsodium hydroxide solution. The resultant dyestutf is salted out withpotassium chloride, washed with a 20% potassium chloride solution anddried at 40 C. in a vacuum. The dyestuff obtained i i y I SOaH Hols0on1.

N 0 1 111 1 a CHz.NH

N i F 1130* l SOaH dyes wool in clear blue shades fast to wetprocessing.

7 EXAMPLE 4 100 parts by weight of a cotton fabric are padded on thefoulard at room temperature with an aquesous solution containing 2% ofthe dyestuff corresponding to the formula of this example, 15 g./1itresodium hydrogen carbonate and 150 g./liter urea, intermediately dried,

7,8 parts1-amino-4-(3'-N-methylaminomethyl-2,6-dimethylanilino)-anthraquinone-2,6,5'-trisulphonicacid are acylated in 85 parts of water at 2025 C. with 3.0 parts2,4-d1fluoro-6-fl:methoxyethoxy-tr1az1ne. pH value of 5 heated at C. for30 seconds then rinsed and soaped 6 to 1s mamtamed during the reactionwlth 2 N at the boil The fabric is dyed in very clear blue shades sodiumcarbonate solution. Before rapidly adding 20 parts fast towet'processing 2f iterates ifiii l iaifiriiisifiiili; 50 of a 10Msoliution y 10 containing 1.5 g. of the dyestuff corresponding to theThe rsultant d esmfi formula of this example, by adding 50 g. of commonsalt y in several portions at 20 to 30 C. in the course of 30 minutes,followed by the addition of 20 g. sodium carbonate and treatment at thesame temperature. After rinsing, soaping at the boil, and drying, a bluedyeing IITHZ of good fastness to wet processing, rubbing and light isobtained.

S0311 EXAMPLE 5 H033 O'CHLCHLOCHZ 6.1 parts of1-amino-4-t3'-a-minomethyl-4'-methoxyania Nlino)-anthraqumone-2,6-d1sulphon1c acid are dissolved m g 1 E 65 partsof water and acylated at 20 to C. at a pH value of 6 with 3 parts2,4-difluoro-6-methylamino-triazine. The pH value is adjusted with a 2 Nsodium hydroxide solution. The resultant dyestuff is salted out with 25potassium chloride, Washed with a 10% potassium chlol H ride solutionand dried at C. in a vacuum. The dye- Soa stuff obtained dyes cotton ingreenish blue shades fast to wet processing.

In an analogous matter further valuable reactive dye 30 stuffs can beprepared from the components set out in dyes wool or cotton m clear blueshades which are fast the following table, which dye cotton in thespecified to wet processing. shades:

Dyeing compound Reactive group Shade l-aminoi-(3-aminomethy1-4-methyl-anilino)-anthraquinone-2,5,2-t1isu1ionic acid2,4-difluor0-6-benzylan ino- Gr blue,

t1-amino-4-(3-aminomethyl-4-methyl-anilino)-anthraquinone-2,8-disultonicacid zigi f li igro-eanilino-triazine Do.l-amino-i-(8-amin0methyl-2,6-dimethyl-anilin0)-anthraquin0ne-2,5,8-trisulfonicacid 2,4-difluoro6-o-to1uidino- Bright neutral t bl1-amino4-(3-N-methylamiuomethy14-methoxy-anllino)-anthraquinone-2,7-disu1ionicacid 2,fiiiiiii ro-6-n-buty1amino- Blu e jgreen.

t l-aminoi-(3-N-methylaminomethyl-4-methoxy-anilino)anthraquin0ne-2,5,2-t1isullonie acid ZA d ii i I iSrO-(i-(N-mcthyl-N-Do.

I phenylamino)-triazine.1-amir1o-4-(3-aminomethyl-anilmo)-anthraqumone-2,8,2-trisulfinic acid2,4-difluoro-G-m-ehloranilino- Greenish bluc.

t"1-amino-4-(3-aminomethyl-4-methoxy-anilino)-anthraquinone-2,7,2-trisulionicacid 2,4 -ii iii ii ro-dbenzylamino- Do.

triazine.

In an analogous manner further valuable reactive dye- EXAMPLE 6 stuffscan be prepared from the components set out .in the following table,which dye Wool and cotton in the speci- V0 9.8 parts1-amino-4-(4'-amino-anilino)-anthraquinonefied shades: 0 2,5-disulfonicacid are acylated in 100 parts of water at Dyeing compound Reactivegroup Shade1-amino-4-(3-N-methylaminomethyl-2,6-dimethylanilino-anthraquinonea,7-disulphonieacid 2,4-difiuoro-6-methoxy-triazine. Blue.

l-amino-4(3-N-methylaminomethyl-2,6'-dimethylaniline)-anthraquinone2,7,5-trisulpl1onic acid 2,4-difluoro6-phenyl-triazine o.

l-arnino t-(3-amino-2'-methylanilino)-anthraquinone-2,6,5-trisulphonicacid Zi-difluoro-dphenylamino- Greenish blue.

rlazme.

When cellulose fabrics are printed with a printing paste 20 C. and at pH5.0 with 4.5 parts 2,4-difluoro-6-anilinowhich contains, per kilogram,15 grams of the dyestuif triazine. When the reaction is completed, thedyestuff is of the formula of this example, 100 g. urea, 300 ml.precipitated by the addition of sodium chloride, filtered Water, 500 g.alginate thickening (60 g. sodium alginate off with suction, washed witha 2 percent sodium chloride per kg. thickening) and 20 g. sodiumcarbonate, and solution and dried at 60 C. in a vacuum. The dyestufiwhich was made up with water to 1 kilogram, dried, dyes cotton accordingto the method of Example 4 in an steamed at 10 C. for 2 minutes, rinsedwith hot water analogous manner, the amino-anthraquinone derivatives andsoaped at the boil, then an intense blue print of good- A and thereactive components B set out in the following fastness to washing andlight is obtained. table can be converted into similar blue dyestufis:

A B Shade 1-amino-4(4'-amino-anilino)-anthraquinone-2,5-disulf0nic acid2,4-difluoro-6-benzylamino-triazinc Greenish blue.

1-amino-4-(4-amin0-anilino)-anthraquinone-2,fi-sdiulfonic acid2,4-dif1uoro-6-n-butylamino-tiiazine Greenish blue.

1-amino-4-(2-methyl-3-amino-ani1ino)-anthraquinone-2,5,5-t1isulfonicacid 2,4difluoro-G-anilino-triazine Bl e,

l-aminoi-(4-amino-anilino)-anthraquinone-2,5,3-trisulfonic acid2,%-difluor0-6-(N-Inethyl-N-phenyl-amino)- Grcem'sh blue.

nazme.

l-aminoi-(4-amino-anilino)-anthraquinone-2,5,3-trisulfonic acid2,4-difluoro-6-benzylarnino-triazine Greenish blue.

1-amino-4-(4-methylamino-methyl-anilino)-anthraquinone-2,5,3-t1isull0nicaeid2,4-difiuoro-6-anilion-triazine Blue.1-amino-4-(4-amino-aniline)-anthraquinone-2,6,2-t1isulfonic acid2,4-difiu0r0-6-n-butylamino-triazine Greenish blue.

9 We claim: 1. An anthraquinone reactive dyestuft having the formula NHR1 I $0311 R2 l R4 R N N a I 0 NH (CH2),11TI Ra a R1 R wherein R and Rrepresent independently of one another hydrogen or hydroxyl, aminoornsulfonic acid;

R stands for hydroxyl, amino or sulfonic acid;

R stands for hydrogen, sulfonic acid, lower alkyl, lower alkoxy orhalogen; R R and R stand independently of one another for hydrogen,lower alkyl, lower alkoxy or halogen;

n stands for the number 0, 1 or 2;

R stands for hydrogen or lower alkyl; and

R stands for amino; lower alkylamino; dilower alkylamino; hydroxy loweralkylamino; di-(hydroxy lower alky1)-amino; phenylamino; phenylaminosubstituted by a member selected from the class consisting of sulfo,chloro, methyl and nitro; benzylamino; hydrazine; lowe'r alkoxy;benzyloxy; lower alkoxy substituted by lower alkoxy or hydroxy; phenoxy;sulfphenoxy; lower alkyl thio; lower alkyl thio substituted by hydroxy;phenylthio; phenylthio substituted by a member selected from the classconsisting of chloro and sulfo; lower alkyl; phenyl; or phenylsubstituted by a member selected from the class consisting of chloro,methyl, nitro and sulfo; and v F stands for a fluorine substituent.

2. An anthraquinone reactive dyestutf of claim I having the formulawherein R; represents hydrogen or sulfonic acid;

R' denotes hydrogen or sulfonic acid;

R and R stand independently of one another for hydrogen, lower alkyl,lower alkoxy, or halogen;

q stands for the number 1 or 2;

R stands for hydrogen or -CH;;;

F stands for a fluorine substituents; and,

R' stands for lower alkylamino having 1 to 4 carbon atoms; lower alkoxysubstituted lower alkoxy; lower alkoxy; phenylamino; sulfo phenylamina;disulfophenylamino; or benzylamino; wherein the lower alkoxy residueshave 1 to 3 carbon atoms.

3. An anthraquinone reactive dyestutf of claim 1 having the formula R4in which R' represents hydrogen or a sulfonic acid group,

R represents hydrogen, lower alkyl, or a sulfonic acid group, R standsfor hydrogen or lower alkyl, R repre- 0 sents phenylamino,sulphophenylamino, lower alkylami- 4. The dyestuff of claim 1 having theformula i w SO3H 1 l V N N Hot t mtgyml s o an 5. The dyestuff of claim1 having the formula it r SO3H i I s 0 H F n 3 I Hots o HN 40 (3H3 IIH-KN JOCHz-CH2OCHa 6. The dyestuff of claim 1 having the formula t 7 Asour 1 N N II I 0 HNNHlN JNHCHzCHz-CH2OH:

HOa S 7. The dyestuff of claim 1 having the formula (EH3 N l H038 CH3orn-N- \N n I T 0 HN o-om-om-owm 8. The dyestuff of claim 1 having theformula t e A -s03H Ho s so H F ll 1 a I 0 HN- I l CH3 NH N NH 12. Thedyestuif of claim 1 having the formula 13. The dyestuif of claim 1having the formula 10. The dyestufi' of claim 1 having the formula H V NF m IN M C N ll C w a a m w m m N E 0 6. O H 0 5 2 2 F H IN J a V H G N.r mi 0 5 m N N H 0 HO UNITED STATES PATENTS 2,889,323 6/1959 Heslop260249 30 3,065,191 11/1962 Heslop et a1. 260-249X 3,251,844 5/1966Singer et a1. 260249x 3,415,825 12/1968 Buchlel et a1. 260-249 11. Thedyestufi of claim 1 having the formula FOREIGN PATENTS m ".1 .m w m mymmum .m mam mm mA I: w m OYO aw HEM HI 5 a V /ll P. H m wc U.S. C1. X.R.

3, 558,620 Dated January 26 1971 Patent No.

HansSamuel Bien, Burscheid, Erich Klauke, Odent Inventor(s) It is,certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 1 1st form.

R5 R I should be 1 46 .contains by. should be .contains, by.

l 63 "vauable" should be --valuable PAH . I page UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION 3,558,620 Dated January 26, 1971 PatentNo.

Hans-Samuel Bien,

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 3 First Form.

A should be 3 52 "tetraflurobortes" should be tetrofluoroborates-.

UNITED STATES PATENT OFFICE Page 3 CERTIFICATE OF CORRECTION InVentor(s)Hans-Samuel Bien,et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 6 lst Formula "O.CH .CH .OCH should be --O.CH .CH .OCH

8 2 "aquesous" should be --aqueous-.

9 73 "phenylamina" should be --phenylamino l0 Claim 5 dependency ofClaim 5 should be 2 instead of "1" l0 Claim 7 dependency of Claim 7should be 3 instead of "l".

10 Claim 8 dependency of Claim 8 should be 3 instead of "1''.

ll Claim 10 dependency of Claim 10 should be 1 instead of "l" ll Claim11 dependency of Claim 11 should be 2 instead of "l".

UNITED STATES PATENT OFFICE I Page 4 CERTIFICATE OF CORRECTION PatentNo. 1; 55 520 Dated January 25 191] Inventor(s) Hans-Samuel et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 11 3rd Form. HHZ

H035- I 50 11" should I ll 0 I N- Signed and sealed this 16th day of May1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. R0 BERT GOTT SC HALK Attesting OfficerCommissioner of Paten'

